Binary and Ternary Systems of Acetone, Methyl Ethyl Ketone, and Water

1872 I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y Vol. 44, No. 8

(13) R a r r , A. E.. Scheibel. E. G.. Rowes. W. 31,. and Othmer . D. 12.. LITERATURE CITED

(1) Bergstrom, as quoted by Hausbrand, E., ”Principles and Prac- tice of Industr ia l Disti l lat ion,” 4th ed., p. 238, New I-ork, C h a p m a n and Hall , 1925.

(2) Blacher, a s quoted by Hausbrar id , E., I h i d . , p. 238-42. (3) Cornell, L. W., aiid Montanna , R. E., IND. ENG. CHEii., 25,

(4) Fenton, T. M., and Garner , W. E., J . Chem. SOC., 1930, 694. (5) Garwin, L., and Hutchison, K . E., IND. ENS. CHEM. , 42, 727

(6) Gilmont. R., IND. ENG. CHEM., ANAL. E D . , 18, 633 (1946). (7) Gilmont, R . , Ph .D . thesis, Polytechnic Ins t i tu te of Brooklyn,

(8) Gilmont , R., and Othmer, D. F., IND. EBG. CHEM., 36, 1061

(9) Gilmont, R., Weinman, E. A, Kramer , F., Miller, E., Hashmall ,

(10) Herman , R. C., aiid Hofstadter , R., J . Chem. Phys., 6 , 534

(11) .Johnson, E. IT., arid Nash, L. K . , J . Am. Chem. SOC., 72, 547

(12) Kahlbaum and Konowalow, “Internat ional Critical Tables .”

1331 (1933).

(1950).

June 1947.

(1944).

F., and Othmer, D . F., I b i d . . 42, 120 (1950).

(1938).

(1950).

Vol. 111, p, 306, S e w Tork, McGraw-Hill Book Co., 1928.

IND. E m . CHEW, 43, 961 (1951).

of S team,” New Tork, John Wiley 8: Sons, 1936. (14) Keenan, J, M.. and Keyes, F. G.. “Thermodynamic Propertlcs

(15) MacDougall , F. H., J . Am. Chem. Soc., 58, 2585 (1936). (16) Othmer, D . F., Anal. Cheiia., 20, 763 (1948). (17) Othmer, D . F., IND. ENG. CHElx., 20, 743 (1928). (18) Ibid., 35, 614 (1943). (19) Othmer, D. F., IND. E X G . CHEM., ANAL. ED., 4, 232 (1932). (20) Obhmer, D. F., and Gilmont, R., 1x0. ENG. CHEM., 36, 858

f 1944). (21) Ibid., 40, 2118 (1948). (22) Othmer, D. F., and Moiiey, F. R.. Ih id . , 38, 751 (1946). (23) Pascal, P., Dupuy . E , and Gainier , Bull. SOC. chim. France 29,

9 (1921). (24) Povarnin, G., and Markoi-. V., J . Russ. Phys. Chein. Sac., 55, 381

(25) Rayleigh, Phil. MuO., 4, Yo. 6, 521 (1902). (26) Ri t te r , H . L., and Simons, J. H., J . Am. C h e m Soc., 6 7 , 757

(27) Sorel, E., Compt . r e n d . , 122, 046 (1896). (28) York, R., Jr., and Holmes, R. C . , IND. ENS. CHEar., 34, 346

(1 924).

(1945).

(1942).

RXEIVED for review March 1, 19.51, ACCEPTED February 21 , 19.52.

(COMPOSITIOS OF VAPORS FROM BOILI-NG BINARY SOLL-TIOll;S)

Binary and Ternary Systems of Acetone, Methyl Ethyl Ketone, and Water

DOSALD F. QTHMER, MANU M. CHUDGAR, AND SHERSI.4N L. LEVY Polytechnic Inst i tute of Brooklyn, Brooklyn, N. 1..

Tu’ T H E commercial synthesis of methyl ethyl ketone, acetone I is produced as a concomitant product; water is also present. Vapor-liquid equilibrium data are necessary for the separation of this mixture by fractional distillation as a step toward manu- facturing high purity ketones. Furthermore such data were de- sired because of the interesting thermodynamic properties of this system.

APPARATUS AND OPERATIhG PROCEDURE

An equilibrium still of the recirculating type which has been developed during the past 20 years for studying phase relations was fabricated from Type 316 stainless steel to permit studies to be made a t pressures up to 500 pounds per square inch absolute. The design and operation of this equipment have been described in a previous paper (17‘).

The operating procedure was similar to that for the standard glass equilibrium still ( l a ) and has been discussed (f7). Particu- lar reference has been made (6) to the supplying of external heat to eliminate radiation losses; this is particularly necessary under the high temperatures encountered here. Pressure was measured with a combination of a dead-weight tester in series with a dif- ferential mercury manometer, and LYas controlled by balancing the heat input and output (17 ) . Temperatures a t the v a r i o u s points of the system were measured with 20 B. &. S. gage iron- constantan thermocouoles which were accurate within h 0 . 3 ‘ C.

the glass vessel used for aiialysis. They were made of xat,er- jacketed copper tubing, having an inside diameter of 4 mm., and Tyere connected directly to the out,lets for sampling boiling liquid and condensate. These were cooled with ice water. About 25 1111. of cold samples were collected for analysis in test tubes immersed in a mixture of ice and water. This met,hod of sampling was checked in the miscible region of the methyl et,hyl ketonewater system a t 100 pounds per square inch absolute by redetermining the vapor liquid equilibrium curve obtained with the use of sample bombs. An excellent check was obtained.

PERFORMANCE OF THE EQUILIBRIUM STILL

Tests were run for possrblc entrainment a t each of the fivc pressures studied. The still was charged with a highly colored solution of methyl orange of a known concentration. The vapor condensate sample was collected as in an actual run and exam- ined in a spectrophotometer. From a calibration curve of standard samples, the concentration of methyl orange in the distillate n-as determined. It was found that the entrainmcnt was only 0.014% of the condensate, which is insignificant.

The experimental data for the system methyl ethyl ketone- water a t atmospheric pressure n ere compared with those of the literature (13, 23) in Figure 10. The agreement is within the limits of analytical accuracy.

Previous investigators ( 1 7‘) have used sample bombs to collect for analysis samples of the two phases in equilibrium. For the systems methyl ethyl ketone-water and acetone-methyl ethyl

MATERIALS USED

Commercial grade synthetic acetone was dried with anhydrous calcium chloride to remove water or lower alcohols and distilled

of the total mas collected a t a constant boiling temperature.

distilled as required, and the refractive index and density of each batch were checked before use. Distilled x-ater from the labora-

pheric boiling points, refractive indices, and densities for t h r acetone and Table I.

ketone-water, there is a range of compositions where either the liquid or the vapor rium temperature but immiscible a t room temperature. In this hiethyl ketone was purified. The range, an error would be introduced by using sample bombs because of the separation of the mixture into two phases upon cool-

n.alls while emptying the bombs. To circumvent this difficulty, small coolers nere used to allow the sample to be taken directlv in

or both is miscible at the equi]ib- in a batch-rectifying column. .4 middle portion comprising 80%

ing and subsequent disproportionate adherence of droplets on the tory &’as used without further purification. The atmoe-

ketone used in this wOr]i arc givPn

August 1952 I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y 1873

TABLE I. PHYSICAL PROPERTIES OF MATERIALS USED Boiling Pt. , O C. a t

760 Mm. Density, d i n Refractive Index, n"D" Obsvd. Lit. Obsvd. Lit. Obsvd. L i t .

Acetone 5 6 , 1 8 56 .50 (26) 0,7848 0.7849 (6) 1.35636 1.3566 (86)

Metliylethylketone 79 62 79 .57 (9) 0 .7998 0.7995 (25) 1.37653 1.37616 (6) 5 6 , l O ($7)

c

,9400

- $ 9000 - 2

0 8600

Y

l200

,7100 IS600 136000 138400 136800 131200 137600 138000

R E F R A C T I V E I N D E X . SOLUBIL,Ty D A ~ A

Figure 1. Analytical Chart for System Acetone-Methyl Ethyl Ketone-Water

ANALYTICAL RIETHODS

I Refractive index and density were the two physical properties used in the analysis of the systems studied. The temperatures for all analytical determinations were controlled to h0.05 C.

ACETONE-METHYL ETHYL KETONE. This system was analyzed by the determination of refractive index a t 25 ' C. using a Bausch and Lomb dipping refractometer. The precision of the measurements was within f0.00004, which corresponds to an analytical precision of 5 0 . 2 mole %. Refractive index-composition data for binary mixtures of acetone and methyl ethyl ketone are given in Table 11.

TABLE 11. REFRACTIVE INDICES OF ACETOSE-METHYL ETHYL KETOXE h/IIXTURES AT 25" c.

Acetone, Wt. Refractive Index, n g 3 . 7 8 7 . 4 5

13 .58 1 9 , 2 4 24 .38 32 .20 36.66 37 .55 4 3 . 9 4 4 8 . 8 4 56 .06 66 .43 6 7 , 2 5 74 .57 81 .52 8 5 . 7 4 88.56 95.81

1 ,37579 1 ,37509 1.37383 1 .37269 1.37158 1.37003 1 ,36907 1 ,36887 1 ,36759 1.36658 1 ,36497 1.36283 1.36272 1.36127 1,35989 1.36890 1.35843 1.38693

ACETONE-WATER. This system was analyzed by the determination of density a t 25" C. using capillary-arm pycnometers (8). The precision of the density measurements was 10.0003 gram per ml., which corresponds to an analytical precision of f 0 . 2 weight %. Squibb's data on the densities of acetone-water mixtures (24 ) were checked and used in this investigation.

weight '% and 88 to 100 weight %, this system was analyzed by the determination of density a t 20' C. using capillary-arm pyc-

3fETHYL ETHYL KETONE--WbTER. In the ranges Of 0 to 17

nometers. The compositions were calculated using the published relations between composition and density (25). These equations are accurate within their respective ranges to 0.05 weight % of methyl ethyl ketone. The density measurements were precise to 0.0003 gram per ml., which corresponds to a precision of f 0 . 2 weight yo.

A known auantitv of water was added to the samples in the range of i 7 to 27 weight % of methyl ethyl ketone to bring the composition within the range of the above- mentioned equations.

Samples in the immisciblc region Bere received directly in burets with their ends sealed off a t the 50-ml. mark. The burets were stoppered and kept in a thermostatically controlled water bath a t 20" C. From a knowledge of the solubilities and densities of each of the two phases, the over-all composition was calculated by reading off the volumes of the two settled phases in the burets. The solubility of methyl ethyl ketone in the water-rich phase was 26.5 weight % a t 20" C. and 87.5 wcight % in the methyl ethyl ketone-rich phase. These values are in excellent agreement with the previously published data (4 23). The densities of the two coexistent liquid phases at 20" C. were determined as 0.8360 for the methyl ethyl ketone-rich phase and 0.9630 for the water-rich phase.

This system was analyzed by the determination of the refractive indices and the densities of the samples a t 25" C. Synthetic mixtures a t 10 weight yo intervals &-ere carefully weighed on an analytical balance. Their refractive indices and densities are given in Table 111. These data were plotted as a composition grid with refractive index and density as coordinates as shown in Figure 1. Liquid-liquid equilibrium and tie line data for this system were determined at 25' C. and are given in Tables IV and V and Figure 2. The tie-line data were correlated by the method of Othmer and Tobias (19) with good results. The plait point was

ACETOKE-METHYL ETHYL KETONE-WATER

M E K W T . % W A T E R - WATER

Figure 2. Mutual Solubility Curve for System Acetone-Methyl Ethyl Ketone-Water i n Weight

Units a t 25" C.

estimated by the method of Treybal et al. (28). The refractive index and density of each experimental point on the boundary curve in Figure 2 were also determined for use in constructing Figure I, which is a plot of liquid composition versus refractive index (ng) and density (d?f'). Figure 1 inset shows that beyond 50 weight % water the grids tend to pinch out, resulting in poor analytical accuracy. A known amount of acetone was added to those samples containing more than 50 weight % water in order to bring them into the region of satisfactory analytical accuracy.

A plot of refractive index against weight yo methyl ethyl ketone with weight % water as the third parameter was constructed. A plot of density against weight yo water with weight '%methyl ethyl ketone as a third parameter was also constructed. By referring to these two plots, a grid work was ruled on a great enlargement of Figure 1 at intervals of 2 weight % for use in analysis. The accuracy of the ternary analysis was checked with synthetic mixtures and was found to be better than 1 weight yo for each component.

1874 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY Vol. 44, No. 8

TABLE 111. DENSITIES A S D REFRACTIVE IXDICES O F A4CETONE- METHYL ETHYL KETONE-WATER SOLCTIOXS AT 25' C.

Acetone, hlEK", Wt. % Rt . % 100.0 . . 90.0

80.0

69.9 10 .1 70.0 60.0 30:O 60.0 20.0 60.0 10.0 60.0 50.0 40:O 49.9 30 .1 50 .0 20 .0 50.0 10 .0 50 .0 40.0 5 0 : O 40.1 39 .9 40.0 30.0 40 .0 10.0 40 .0 . . 29.9 60.1 29.9 50.1 30.0 40.0 30.0 30.0 30.0 20.0 30 .0 10 .1 30 .0 20 .0 70:O 20 .0 60.0 20.0 50.0 20.0 40.0 20.0 30.0 20.0 20.0 20.0 11.0 79:l 10 .1 30 0 10 .0 19.9 10.0 10 .0

80.0 10:o

70.0 20: 0

10.0 . . 90: 0 1 . 20.0 . . 10.0 . . 100 0

a Methyl ethyl ketone

Water, Wt. %

10: 0 10 .0 20 .0 1 0 . 0 20.0 30.0 10.0 20.0 30.0 40.0 10 .0 20.0 30.0 40.0 50.0 10.0 20.0 30 .0 50 .0 60.0 10.0 20 .0 30.0 40 .0 50.0

70.0 10.0 20.0 30.0 40 .0 50.0 60 .0 80.0 9 .9

59 .9 70.1 80.0 90 .0 10.0 80.0 90.0

;9,9

. .

Density, d i 5

0.7848 0.8146 0.8161 0.8432 0.8169 0.8435 0.8695 0.8188 0.8440 0.8696 0 8942 0,8200 0.8454 0.8695 0.8939 0.9159 0.8209 0.8460 0.8693 0.9153 0.9361 0.8221 0.8468 0.8705 0.8938 0.9153 0.9355 0.9537 0.8234 0,8477 0.8697 0.8930 0.9150 0.9359 0.9700 0.8244 0,9347 0,9540 0.9700 0.9831 0.8260 0.9707 0.9840 0.7998

Refractive Index, n%

1.35636 1.36020 1.36218 1.36270 1.36421 1.36465 1.36348 1.36632 1.36627 1.36515 1 ,36283 1.36819 1.36813 1,36681 1,36444 1.36078 1 ,37020 1.37000 1.36842 1.36236 1 ,36745 1.37210 1.37179 1.37017 1.36755 1,36390 1.35902 1.35272 1.37399

1.33983 1 ,37779 1.36026 1,34169 1.37653

~

VAPOR CORlPOSITION DATA

ACETONE-METHYL ETHYL KETONE. The experimental vapor- liquid equilibrium data for this sytem at pressures of 14.7, 50, 100, 250, and 500 pounds per square inch absolute are presented in Table VI and Figures 3 and 4. This system was found to be ideal within the experimental error a t all pressures up to 500 pounds per square inch absolute.

ACETONE-WATER. The experimental vapor-liquid equilibrium data are presented for this system at 14.7, 50, 100, 200, 250, and 500 pounds per square inch absolute in Table VI1 and Figures 5 and 6. The data a t 14.7 pounds per square inch absolute are compared with those of other investigators (g , 13, 16, SO) in Figure 7. There is good agreement between the authors' data and those of York and Holmes (SO). The authors' data have been tested for

TABLE Iv. LIQUID-LIQVID SOLUBILITIES O F TERKARY SYSTEM ACETONE-METHYL ETHYL KETONE-WATER .4T 25" c.

~ ~ ~ t ~ ~ ~ , MEKO, ~ ~ t ~ ~ , Density, Refractive Index, wt. % Wt. % Wt. % dZ5 n"D"

87 .4 12.6 0.8312 1 ,37742 3 : 2 83.4 13.4 0.8333 1.37702 7 .1 76.7 16.2 0,8404 1.37620 8 . 0 75.0 17 .0 0.8425 1.37600

10.1 70.1 19.8 0.8490 1.37531 12 .0 63.6 24.4 0.8596 1.37410 12.4 58 .5 29.1 0.8690 1 37292 12 .5 56 .5 31.0 0.8735 1.37266 12 .5 49.9 37.6 0.8870 1.37100 12.1 46.4 41.5 0.8950 1.36982 11.4 39.6 49.0 0.9107 1.36713 9 .9 34 .5 55.6 0.9233 1 ,36455 8 . 1 30.6 61.3 0.9349 1.36190 4 .5 26 .5 69 .0 0.9515 1.35800 . . 24.8 75.2 0.9618 1.35461

11.1 37.9 51.0 Estimated plait point (88) 0 Methyl ethyl ketone.

thei-modynamic consistency at all the pressures investigated by the method of Redlich and Kister (98) with satisfactory results. A comparison of the authors' data with previous data a t 14.7, 50, 100, and 200 pounds per square inch absolute shows deviations larger than can be accounted for by analytical error. This is probably caused by some rectification of vapors in the previous work (16). The wide difference in volatilities between these two liquids accentuates the difficulties in preventing change in composition of the vapors after a steady state a t the liquid interface has been reached.

The experimental .vapor- liquid equilibrium data for t,his system are presented at 14.7, 50, 100, 250, and 500 pounds per square inch absolute in Table VI11 and Figures 8 and 9. The data a t 14.7 pounds per square inch absolute agree within the analytical accuracy with those in t,he literature (13, 23), as sho~vn in Figure 10.

The system methyl ethyl ketone-water is incompletely miscible over a part of the range of liquid compositions a t the boiling temperatures corresponding to 14.7, 50, and 100 pound8 per square inch absolute. Experimental data were taken in the hetero- geneous region; the terminal liquid compositions for the hvo- phase regien were determined from published mutual solubility data for methyl ethyl ketone and water a t high temperatures (93). The solubility limit curve on Figure 8 was then drawn with the horizontal line of each vapor composition curve representing the corresponding parameter of temperature. A smooth, flat U- shaped curve results with the plait point at the temperature of complete solubility. There has already been discussed ( I S ) the interesting relation of the mutual solubility to the left of the 45' line, the horizontal line which does not cross the 45' line, and

METHYL ETHYL KETONE-WATER.

100

90

80

a 0 70 a 60

z

a >

zww Q 14.? R S I h 0

k y 40 a 8 j 30 0 z 20

I O

0 0 IO 2 0 30 40 50 60 70 88 9 0 100

MOL. % ACETONE IN L I Q U I D

Methyl Ethyl Ketone at Various Pressures Figure 3. Vapor-Liquid Equilibria for System Acetone-

TABLE V. LIQCID-LIQCID SOLUBILITIES o r TERXARY SYSTEM ACETOXE-~IETHYL ETHYL KETOKE-\y7-4TER AT 25' c.

(Tie-line comnositions) Solvent Layer Water Layer

Acetone, MEKa, Water, Acetone, L'IEKQ Water, wt. % Wt. % nt . % wt. % wt. % wt. %

2.0 1 .4 3 .7 6 .1 8 . 2

10.7

85.0 85.8 82.6 78.7 74.5 68 .3

13 .0 12 .8 13 .7 15 .2 1'7.3 21.0

1 . 7 1 . 2 3 . 3 4 .7 6 . 0 7 .8

25.2 25.1 25.8 26 .6 28.1 30.5

73 .1 73.7 70 .9 68 .7 65.9 61.7

Methyl ethyl ketone.


4

M O L . % ACETONE

Figure 4. Temperature-Composition Diagram for Sys- tem AcetoneMethyl Ethyl Ketone at Various Pressures

TABLE VI. VAPOR COMPOS~TION DATA FOR ACETONE-METHYL ETHYL KETONE AT VARIOUS PRESSURES

(Experimental data)

Mole % Acetone Temp., Liquid Vapor ' C. Liquid Vapor O C.

14.7 Lb./Sq. In. Abs.

Mole % Acetone T ~ ~ ~ . ,

250 Lb./Sq. In. Abs. 95.0 97.2 89.1 94.2 81.7 90.3 73.8 85.7 72.7 84.0 68.6 81.7 67.6 81.7 62.0 77.5 54.4 71.5 51.0 65.7 45.0 64.0 37.3 57.1 24.5 43.7 15.3 29.0 8 . 1 15.3 2 . 6 5.0

50 Lb./Sq. In. 90.9 94.6 81.0 89.2 67.3 80.5 58.8 74.4 57.4 73.5 45.3 62.5 42.0 59.3 38.8 56.4 29.6 46.3 20 .8 35.0 16.9 30.2 13.3 24.7 7.6 13.0 1 .9 3.7

56.9 57.9 58.9 60.0 60.3 61.0 61.1 62.1 64.1 65.1 - 67.0 69.0 71.4 74.2 76.6 78.5

Aba.

92.9 95.1 175.1 84.3 87.7 175.0 72.6 78.8 178.9 69 .1 75.7 180.0 61.8 70.4 W3.2 54.3 63.0 186.1 44.6 54.5 188.9 36.4 45.9 191.5 33.1 41.8 193.1 29.2 38.5 194.0 19.8 27.5 197.5 13.2 19.4 199.5

1.9 2.9 203.5

500 Lb./Sq. In. Abs. 95 .5 97.1 214.5 91.3 93.3 215.6 85.5 88.1 218.0 79.5 83.0 220.1 71.3 76.1 222.6 70.1 75.7 223.2 65.0 69.1 225.0 57.0 62.2 227.4 39.7 45.0 233.5 33.5 38.3 235.6 25.2 29.5 238.9 19.0 22.3 241.4 15.1 18.6 243.0 6 .2 8 .6 247.8 5.0 7 . 8 248.4

100 Lb./Sq. In . Abs. 92.0 95.4 127.5 82.7 89.5 129.2 71.3 81.5 131.7 68.7 80.2 132.8 58.9 73.0 134.7 51.5 66.8 137.3 44.0 60.3 139.3 35.4 51.2 141.7 29.6 44.3 143.1 19.4 31.5 147.1 14 .7 25.7 148.9 10.3 19.0 150.6 7.6 12.4 152.0 1 . 9 3.5 153.3

TABLE VII. VAPOR COMPOSITION DATA FOR ACETONE-WATER AT VARIOUS PRESSURES

(Experimental data)

Mole % Acetone T ~ ~ ~ . , Mole % Acetone T ~ ~ ~ . , Liquid Vapor O C. Liquid Vapor C.

14.7 Lb./Sq. In. Abs. 200 Lb./Sq. In. Abs. 85.0 91.8 57.1 79.3 90.0 57.4 66.1 86.0 58.5 60.9 84.7 58.9 53.8 84.0 59.5 50.6 83.7 59.7 44.4 83.2 60.0 30 .0 80.9 61 .1 26 4 80.2 61.8 12 .0 75.6 66.2 4 1 58.5 76.5 2 .3 46.2 83.0 1 . 0 33.5 87.8

86.3 85.0 157.2 75.2 75.8 157.6 64 .1 69.9 157.8 59.0 66.9 157.9 48.9 63.2 158.4 38.2 59.5 159.1 37.2 59.3 159.9 24.4 56 .1 160.6 17 .5 52.6 162.5 13.6 49.5 163.9 10.8 47.7 164.4 6 . 2 39.7 168.9 2 . 0 28.9 177.2

50 Lb./Sq. In. Abs. 250 Lb./Sq. In. Abs. 95.0 95.1 98.2 89.0 90.3 98.4 77.8 83.0 98.6 63.3 76 .8 98.8 54.5 74.7 99.0 38.8 71.8 99.9 27.3 69.5 101.3 19.4 67.0 102.8 10.7 60.8 106.0 5.5 51.8 112.0 2.4 39.8 120.0 1.7 34.9 122.5

94.7 93.1 170.4 90.3 88.4 169.7 80.9 78.4 168.6 72.2 73.1 168.4 60.8 66.6 168.8 49.4 61.2 170.3 39.1 58.0 170.6 27.4 55.1 172.2 17.6 50.5 174.0 8 . 7 42.3 178.6 4.4 33.5 185.1 1.6 20.6 193.4

100 Lb./Sa. In. Abs. 500 Lb./Sa. In. Abs. 92.5 84.2 75.4 55.9 44.4 34 .1 22.9 14.4 7 . 8 3 .6 1 . 4

. - 91.2 84.5 78.1 70.0 66.5 65.0 61.8 58.2 50.7 39.5 24.9

. -

92.1 85.3 75.0 66.3 58.5 52.7 46.5 40.8 31.8 14.0

MOL.% ACETONE IN L I Q U I D

Water a t Various Pressures Figure 5. Vapor-Liquid Equilibria for System Acetone-

the fact that the crossing of the 45" line-i.e., the azeotropic point-is not a t the steam distillation temperature or composition and the concomitant disappearance of the horizontal section of the curve. The azeotropio temperature, and not the steam distillation temperature, therefore, represents the minimum point on the phase diagram of Figure 9. This indicates an interesting minimum point below the usual line of the steam distillation range.

I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y Vol. 44, No. 8 1876 - TABLE 'I-111. VAPOR CO\.IPOSITION DATL FOR ?~LETHYI, ETHYL

KETOSC--\TATCR AT 'I'ARIOKs PRE55VRES

(Experimental data)

MOL. % ACETONE

Figure 6. Temperature-Composition Diagram for System Acetone-Water at Various Pressures

ACETONE-~~~ETHYL 7 h x I Y L I<EToA-E--\~ATER. The esperi- mental vapor-liquid equilibrium d a b are presented at 14.7, 50, 100, 250, and 500 pounds per square inch absolute in Tables IS to XI11 and Figure 11. The experiment,al data xyere first plotted after the method of Grisn-old and Dinwiddie ( 4 ) ; Figure 11 \vas con- stivcted by cross plotting smooth values from these plots. The triangular plots in Figure 11 show grids of mole methyl ethyl

14.7 Lb./Sq. I n . dbu. 100 L?.&. In. Abs

99.3 96 .3 78 .3 97 .7 92 .9 i 7 . 0 95 .8 8 9 . 8 7 6 . 4 91.2 81 .6 i 5 . 3 8 8 . 0 76 .7 i 4 . 5 8 4 . 8 73 .6 7 3 . 8 83.6 73.8 7 4 . 1 80.3 7 0 . 7 7 3 . 9 80.0 70 .7 73.9 7 8 . 1 69.8 i 3 . 5 77.5 69.6 74.0 74.4 68.3 i 3 . z 7 2 . 9 67.6 7 3 . g 72.1 67.6 7 3 . 8 70.9 6 7 . 1 73.C) 66.7 6 6 . 1 73 .5 66.5 6 5 . 7 73.6 65 5 65.5 73.3 6 3 . 5 65 .4 73 8 5 5 . 0 64.5 i 4 . 4 1 9 . 0 6 4 . 5 7 4 . $ 3 . 6 6 1 . 8 7 J . J 1 . 7 51 .5 s 1 . 2 1.1 39.4 84 .6 0 . 5 20 .7 9 9 . 0 0 . 4 18 .4 03 .2 0 . 2 8 , s 97.(3

50 Lb./Sq. 111. .?il)s. 96.9 91.4 121.0 94.9 86.5 1 1 R '2 91.9 79.7 117 0 90.1 77.5 116 J 89.9 77.3 116 6 86 .6 72.8 116 2 81.3 67 .9 114.9 78 .9 66 .4 114 6 74 .9 63.6 113.0 67.6 59.6 112 3 6 7 . 0 59 .2 112 3

~ 1 . 4 56 .2 112.2 45.0 56.1 112.3 3 0 . 0 55 .6 112.3

1 . 7 50.8 113 1, 1 . 4 51 .6 116.3 0 . 8 3 4 . 8 124 2 0 2 1 4 . 1 i33 1

60.7 5 7 . 8 112.2

a Methyl ethyl ketone.

98 S 93.: 152.2 96 .0 150.5 90 .0 :;.; 147.4 83 .5 68.4 143.5 82.6 66 .7 142 4 72 2 59.6 140.3 60 .0 53.3 139.3 6 3 . i 30.7 139.0 46 5 .51.0 139 2 38.3 5 1 . 7 139 3 33.1 50 .4 139.3 22 0 !SO 9 189.4 1 2 . 0 49 9 139.4 4 6 4 6 . 9 141.9 3 . 0 45 9 1.12 9 1.1 36.3 149.2 0 . 6 L'6.4 155.1 0.1 8 d 162.6

2.50 L b 3,; In. Ab?.

98.9 9 7 . 5 201.6 95.3 88.J 107 5 89.8 79.3 193.4 84 8 7 1 . 0 189.8 76 8 62.6 185.0 7 2 . 9 48.6 184 8 59.9 50.8 181.6 5 8 . 3 j 0 . 0 181.2 48 .6 46 2 180 7 37 .3 43.9 180.7 31.8 1 3 . 8 181 1 18.9 42 .0 182.0 1 1 . 2 42.2 182.4

2 . 9 31 3 186 0 2 . 3 2 6 . 5 189.4 1 . 2 20 9 192.5 0 . 4 3 . 9 200.2

3 . 6 33 2 185.6

500 Lh.;Sq. In. Abs. 94..5 90 .1 242.2 91.7 8 6 . 8 240.0 90.9 86.3 239.4 83.2 7 3 . 5 231 1 77.2 6 7 . 4 226 7 70 .3 ,57.4 223.3 61.9 50 .2 2 1 9 . 4 53.6 46.1 217.2 41 0 40 9 216.1 3 6 . j 39 0 216 5 27 .0 36 6 216.8 18 1 35.2 218 0 8 . 6 28 4 221.1 2 . 1 17 % 227 2 1 1 10 0 233.!4

THIS INVESTIGATION a BRUNJES R BOGART

0 OTHMER R BENENAT 0 OTHMER R MORLEY

YORK R HOLMES

0

MOL.% ACETONE IN LIQUID

Figure 7. System Acetone-Water Comparison of authora' data with that of previous in, ebtigators

100

90

80

a 70 2 a ' 60 z 5 50 5 be 40

Z 30

20

IO

0

0 4 7 P S l A -I 0

0 MOL. M E K IN LIQUID

Figure 8. Vapor-Liquid Equilibria for System \Let115 I Ethyl Ketone-Water at Various Pressures

7

August 1952 I N D U S T R I A L A N D E N G I N E E R I N G

TABLE IX. VAPOR COMPOSITION DATA FOR ACETONE-METHYL ETHYL KETONE-WATER

(At 14.7 pounds per square inch absolute) Liquid Vapor

Acetone, MEKa, Water, Acetone, MEKa, Water, mole % inole % mole % mole '5% mole % mole 70 Temp., C.

74.0 62 .8 61.4 56.2 52 .3 48.1 42.4 42 .0 41.0 40 .0 38 .8 38 .7 37.6 29 .8 29.7 27.3 26 .5 25 .5 20.8 18.2 16 .3 16 .1 15 .9 13 .5 12.7 12 .1 12 .0 11 .6 11 .1 9 . 5

11 .4 13 .2 26 .0 23.2 10 .5 36.0 36 .3 40 .3 25 .3 16.9 24.4 37.4

8 .6 10 .7 4 9 . 5 30 .3 41 .4

5 . 4 35 .3 39 .6

5 . 0 45.7 31 .6

5 . 5 17 .8 25 .3 78.5 57.4 12.0 50 .3

14 .6 24 .0 12.6 20 .6 37 .2 15.9 21 .3 17 .7 33 .7 43.1 36 .8 23.9 53 .8 59 .5 20 .8 42 .4 32 .1 69 .0 43 .9 42.2 78 .7 38.2 52 .5 81 .0 69 .5 62 .6

9 . 5 31 .0 76 .9 40.2

84 .8 76 .9 72 .8 69.2 74.0 61.0 58.1 54.6 60.0 67.2 61 .9 53.9 72 .7 65.3 42.4 47 .5 42 .3 69 .5 39.7 33 .9 62.0 28.7 33 .4 61.4 36.9 27.9 18.7 19 .3 38.6 19 .4

5 .2 8 .8

16.3 15 .4 8 . 3

23.7 24.4 28.2 16 .6 13 .9 18.5 27 .3

9 .4 13 .7 36.6 28.6 33 .3 10 .3 34 .4 37 .9 14.8 43 .4 38.6 20.2 35.2 40.6 6 4 . 0 51 .5 33.2 52.8

10 .0 14 .3 10.9 15 .4 17 .7 l 5 , 3 1 7 . 5 17 .2 23.4 18 .9 19 .6 18 .8 17.9 21.0 21.0 23.9 24 .4 20.2 25 .9 28.2 23.2 27 .9 28 .0 18 .4 27.9 31 .5 17 .3 29.2 28.2 27.8

58.3 59.9 62.1 62 .5 61.8 65 .8 66 .8 66 .7 64.9 63 .8 65 .0 67.2 63.9 64.7 67.8 67 .3 67 .8 64.6 68 .3 68.4 66.2 71.2 69 .9 6 6 . 8 67.5 69 .7 72.3 78 .3 67 .8 71.4

8 . 9 42 .0 49.1 ' 8 . 5 48.7 42 .8 71 .3 8 . 2 13 .9 77 .9 28.5 42 .0 29 .5 69 .8 7 . 9 9 . 3 82 .8 35.5 35 .8 28 .7 69.4 7 . 1 89.9 3 . 1 12.8 76.1 11 .1 77.0 5 . 5 3 . 9 90.6 50.2 24.1 25.7 73 .1 4 .7 36.9 58.4 11 .3 56.1 32 .6 72.9 2 . 2 8.0 89 .8 17 .5 48.6 33.9 79 .5


ketone and mole yo acetone in vapor superimposed over a grid of liquid compositions expressed in mole %; mole water in the vapor is obtained by difference.

Since vapor pressure data are necessary for correlation pur- poses, these were determined for acetone and methyl ethyl ketone in the equilibrium still and are given in Table XIV. These were

M O L . Ye M E K

Figure 9. Temperature-Composition Diagram for Sys- tem Methyl Ethyl Ketone-Water at Various Pressures

At moderate

C H E M I S T R Y 1871

tested by plotting on a logarithmic reference plot (IO). Excellent agreement was obtained with the best literature data for acetone (25) . The vapor pressure data for methyl ethyl ketone above 14.7 pounds per square inch absolute could not be found in the literature. The de- t e r m i n e d t e m p e r a t u r es are precise n-ithin 1 0 . 3 " C. and the pressures within f 0 . 2 pound per square inch absolute. The vapor pressures of water were taken from published data ( 7 ) , and it had already been shown (17) that this still gave results corresponding to accepted published values.

CONSISTENCY AND CORRELiTION OF DATA

Most methods of testing the consistency of vapor-liquid equilibrium data make use sf activity coefficients which are defined as

71 = "fl/f,".1 (1)

At low pressures and small liquid volumes, the effect of pressure on the fugacity of the liquid may be neglected. If it is also assumed that the vapors behave as ideal gases. Equation 1 may be written

Y1 = p : / . z : = Y l P / X 1 P ? (2)

This equation is expressed in the logarithmic form since log y1 and log yz are usually plotted against liquid composition

( 3 )

pressures, the equation of Benedict et al. (I), IT hich

log Y1 = log(Y,/sl) - log(P:/P)

takes into account the nonideality of the vapors and the effect of liquid volume, was used to calculate the activity coefficients

( P - P,")(+l - P i ) (4) RT log Y1 = log(Yl/zl) - log ( P : / P ) -

Equation 4 was used up to pressures of 100 pounds per square inch absolute, beyond which its use may cause an appreciable error

0 0 IO 20 I 30 I 40 5 0 I 60 70 1 90 I 90 I 100 I MOL. % M E K IN ,LIQUID

Figure 10. System Methyl Ethyl Ketone-Water Comparison of authors' data with that of previous investigators

1878 I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y Uol. 44, No. 8

M E T H Y L

& S T O N E E T H Y L

P R E S S U R E 500 P S I A

ACETONE

20

METHYL ETHYL

KETONE PRESSURE 250 P S I A

ACETONE

'ATER

METH €THY KETONF

PRESSURE 100 P S l A

WATER - KETONF

PRESSURE 100 P S l A

($0). Since the liquid densities of acetone and methyl ethyl ketone at elevated temperatures are not in the literature, 01 was calculated using \I7atson's correlation of liquid densities (29) and & n-as evaluated from Berthelot's equation (21)

The critical constants for methyl ethyl ketone were not available in the literature and ?yere calculated by Meissner's method (IO). Critical data for methyl ethyl ketone have since been published (83) and the calculated values are in excellent agreement with these published data.

For pressures of 250 and 500 pounds per square inch absolute, the activity coefficients were calculated using fugacities. Equa-

0 0

P R E S S U R E 50 P S I A KETONE

ACETONE

WATER -

WATER -9

PRESSURE 14.7 P S I A

Figure 11. Vapor-Liquid Equilibria for System Acetone-Methyl Ethyl Ketone-Water a t Various

Pressures - - - Mole 70 acetone i n vapor

Mole % methyl ethyl ketone in vapor

f-

tions of state are not available for acetone and methyl ethyl ketone. It was, therefore, necessary to use the generalized fugacity charts of Gamson and Watson ( 3 ) . The activity coefficients were calculated for each experimental point for the three binaries a t all pressures. In each case, a plot of log y1 and log y2 versus liquid composition showed excellent consistency except a t extreme concentrations.

The binary data were tested for thermodynamic consistency by the method of Redlich and Kister (22) with satisfactory results in all cases. This method was chosen because of the relative ease of correlating the ternary system once the constants were evaluated for the three binaries. The constants for the Redlich and Kister equation are given in Table XV for the binaries. It was found necessary to use a fourth constant in the case of the methyl ethyl ketone-water system because of its extreme nonideality.

The ratio log y1/y2 was calculated for the solubility limits using the coefficients in Table XV and compared with that obtained from solubility data with the following results:

Lower Solubility Limit Upper Solubility Limit Log yi/yzfrom Log yi/w from

Redlich and Log yi/y2 Redlioh and Log yi /w Pressure, Lb./ Kister (22) from solu- Kister (22) from solu- Sq. In. Abs. constants bility data constants bility data

14.7 1.064 1.043 -0.360 - 0 , 3 0 2 0.963 0.974 -0.0521 -0,053

0 , 2 9 1 50

100 0.774 0.771 0.302


I I I I I I I I I I I I l l l l l l I I1111 OTHMER BENENATI (13)

M E K - WATER

.OOl .o I .IO 1.0

0.7 - I I l l l l l l I I I l l l l l l - I I I I l l i t - - ACETONE - WATER

OTHMER BENENATI (13

1

.oo I .o I .IO 1.0

Figure 12. Log Reduced Total Pressure against Log Reduced Pressure of Water at Same Reduced

Temperatures

The ternary system was also correlated using Redlich and Kis- ter’s method, and all the ternary constants were found to be equal to zero. The vapor compositions for the experimental liquid compositions were then calculated using the ternary equations of Redlich and Kister and compared with the experimental vapor compositions. A preponderant number of calculated vapor compositions ehecked within 2 mole % a t pressures up to 100 pounds per square inch absolute and within 3 mole % at pressures of

IO

i I 1.0

RED. PRESS. WATER 40 I .o I .I,O

1 I I I111111 I I I I l l l l l I I 1 1 1 1 1 1 1 I I IllIl lJ I I l l

.001 .01 .IO 1.0

Figure 13. Log Relative Volatilities of Light Com- ponent with Respect to Heavy Component against Log

Reduced Pressure of Water at Same Reduced Temperature

0 -

0

O THIS INVESTIGATION OTHMER a BENENATI

0 B 10

4 6 8 10 20 40 60 80 100 200 400 600 TOTAL PRESS. PSlA

Figure 14. Log Concentration of More Volatile Com- ponent in Azeotrope against Log Total Pressure

250 and 500 pounds per square inch absolute except a t extreme concentrations.

Previous papers (11,14) developed a general and simple method for correlating vapor-liquid equilibrium data. This method has the advantage of producing linear relationships. It consists of plotting, on logarithmic paper, the various properties of solutions against those of a reference substance, usually water, at the same temperature. This method of correlation tends to Show curvature as the critical region is approached. A more recent paper (16) presents an analogous plot on a reduced reference basis and this method was used to correlate the binary systems. Smooth equilibrium data for all three binaries were read from Figures 3 to 9 and were plotted as reduced total pressure against reduced vapor pressure of water a t the same reduced temperature for various isosteres on Figure 12 and as relative volatility against reduced vapor pressure of water a t the same reduced temperature for various liquid isosteres on Figure 13. The system methyl ethyl ketone-water shows curvature on Figure 13 at liquid compositions greater than 70 mole due to the extreme nonideality of the system. For the systems methyl ethyl ketone-water and

1880 I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y voi. 44, N ~ . a ACKNOWLEDGMEAT

The authors wish to thank the Vulcan Copper and Supply Co. for supplying the equilibrium still described. Thanks are also due to the Carbide and Carbon Chemicals Corp. for supplying the acetone used and to the Shell Chemical Corp. for furnishing the methyl ethyl ketone

T L B T Z x. iPOR COhiPOSITIO\ I> LT.4 FOR ACETOSE--hIETHYL E T H Y L KE10\h-J174TER

(.it 50 pounds pel squa ie inch absolute)

_ _ _ ~ Acetone. niole 'z 83 2 78 i 76 5 72 8 71 .2 68 .5 55 9 G O 0 5 2 . 1 ,54.3

Vapor MEKa, mole 70

4 . 8 10.3 11.1 8 . 5

17.9 8 .1

28.6 14 .2 26.8 1 8 . 7

~~

Liquid MEKa, mole

8 3 18 .6 19.3 1 3 . 0 30 1 10 7 44.3 17.9 41.0 24 .5

Acetone, mole 72

77 4 72 5 67 8 62 3 62 0 52 0 4~5 7 42 8 42 4 41 1

Water, mole %

14.3 8 9

12 9 2 4 . 7

7 . 9 3 7 . 3 1 0 . 0 3 9 . 3 1 7 . 6 3 4 . 4 37 8 4 4 . 8 53.9 50 4 60 .7 4 0 . 8 2 9 . 7 71.2 42 .9 44 6

9 . 0 7 8 . 7 6 5 . 3 53 .2 75.3 70 .5 63.2 31.2 5 8 . 8 8 8 . 6 78 6 50 .2 2 . 3

83 8 68 7 9 1 . 1

Water, mole % 1 2 . 0 1 1 . 0 1 2 . 4 1 8 . 7 10.9 23 .4 15.5 2 5 . 8 21 .1 27 0

Temp., C. 99 1

101 4 100 7 101 2 103 9 101 9 107 2 103 3 106 1 104 1

SOMENCLATURE

= act,ivity coefficient of component 1 = fugacity of component 1 in solut,ion = fugacity of pure component 1 at the t p m -

perature and pressure of the solution = mole fraction of component 1 in t,hc

liquid phase = partial pressure of component, 1 in the

vapor = vapor pressure of pure component 1 at the

temperature of the solution = mole fract,ion of component 1 in the vapor

phase = total pressure = absolute temperature = molal gas constant = molal volume of pure component 1 in the

liquid state = second virial coefficient in the equation

of state of pure component 1 = critical temperature in degrees absolute = critical pressure = relative volatility, light romponmi t,o

38 8 38 4 37 .6 29.1 28 5 2 7 . 7 2 6 . 1 2 3 . 5 20 .1 20 0 1 6 . 5 1 6 . 3 15 .2 1 4 , 4 12 .6 1 1 . 8 1 1 . 6 9 . 3 8 8 8 7 7 . 4 7 . 3 7 .2 6 . 8 5 . 8 1 . 9

23 .4 1 6 . 8 8 . 5

2 0 . 5 10.8 31 .5 44.2

5 . 3 37 .0 35.4 74.5

5 . 0 1 9 . 5 3 2 . 4 1 2 . 1 17 .7 25 .2 59 .5 32 .4

2 .7 1 4 . 0 4 2 . 5 9 0 . 5

9 . 4 25 .5

7 . 0

33 3 5 7 4 63 2 4 8 . 6 5 3 . 3 41 3 37 0 57 4 3 1 . 5 3 2 . 7

18.5 14.4 8 . 2

19 .8 1 3 . 7 26.8 33 .5

9 .5 33.6 3 3 . 0 58.2 12.9 29.4 35.6 26.3 34.7 36.7 50.0 43 .1 11.4 37 .0 45 .4 79.7 31 .9 46.4 39 .8

28 0 28 9 28 6 31 6 32 8 31 9 29 3 33 1 34 9 34 3

105 0 103 3 103 3 105 0 104 4 107 1 108 2 104 1 108 6 108 3

24 3 53 .0 34 .4 28 R 37 .6 30 .7 24.2 15.8 19 .0 50 2 23 4 1 5 . 2 11.5 29 .1 1 5 . 6 1 4 . 8

17 .5 32.1 36 .2 36.4 36 .1 3 4 . 6 3 9 . 1 34 .2 37 9 38 .4 39 .6 39 .4 8 . 8

39 .0 38 .0 45.4

115.2 104 . , 107 .8 109 .1 107 6 108.6 109.2 116.1 111.6 107.1 109.2 107.1 120.0 108.8 112.0 120.0

0 AIethyl ethyl ketone. heavy component

LITERATURE CITED

acetone-water, the previously published subatmospheric data ( I S ) mere found to lie on the same straight, lines as the data of this investigation, indicat,ing good agreement between the two sets of

(1) Benedict, AI., Johnsoil, C . -k., Solomon, E., and Rubin. L. C. .

( 2 ) Rrunjes, A. s., and Bogart, hI. ,I. P., IND. ESG. CHEM., 35, 2% Trans. Am. I n s t . Chem. Engrs., 41, 371 (1945).

11943). data. (3) Camson, B. IT., and Watson, K. XI,, S o i l . P e t r o k w n S e w s 36,

The binarv methyl ethyl ketone-w~ter Ivas found to be azeo- R623 (1944). tropic at all pressures studied, while the system acetone-water exhibited azeotropism at 100 pounds per square inch absolute and higher pressures. The azeotropic data for these systems have been correlated in Figure 14 according to the met,hod of Othmer and Ten Eyck (18).

T'apor-liquid equilibrium data for t,he ternary syst,em were also correlat,ed by means of logarithmic plots. Log mole 70 methyl ethyl ketone in vapor was plotted against log total pressure at constant mole yo water in liquid with mole 70 methyl ethyl ketone in liquid as a parameter. i\lole % acetone in vapor was plott,ed similarly. The data plotted linearly indicating the utilit,y of this type of plotting for correlating ternary vapor-liquid equilibrium data over a n-ide range of pressure.

CONCLUSION s

Consistent vapor-liquid equilibrium dat,a have been presented for the systems acetone-methyl ethyl ketone, a c e t o n e - w a t e r , m e t h g l e t h y l ketone-water, and acetone-methyl et.hyl ketone- n-ater a t pressures of 14.7, 50, 100, 250, and 500 pounds per square inch absolute. Those data lmve been correlated so as to permit rapid and accurate interpolation. Two of the binaries were found to exhibit azeotropisni; t,he azeotropic data were correlated on logarithmic plots.

TABLE XI. VAPOR C:03IPOSITIOS D A T A FOR A%CETOSE-hh?THYI, ETHYL KETOiYE--\\-ATER

(AI 100 pounds per square inch absolute) Liquid

Acetone, hIEK", &-ate;, Acetone, mole % mole R mole 70 mole %

5 . 0 , 1 3 , 9 127,z 11 .6 1 5 . 6 128 ,3 9 . 0 2 2 . 8 127.8 10.8 10 .8 129,3 13 .9 29 .0 130.0 3 0 . 5 16 2 136.4 1 4 . 1 31 . ? 130.8 28 .4 23 .9 134.9 18 .6 32 .2 131.4 19 .7 32 .6 131.9

78 6 68 .1 61 .6 72.6 50.7 45.6 42. J 40 .3 40 .1 3 7 . 3

1: 5 13 .9 19 .4 21 1 45 0 18 .3 42.7 24.0 24.5

12 3 12 4 24 5

8 . 0 28 2

9 4 39 2 17.0 36 9 38 2

81.1 72.8 68.2 78 .4 5 7 , l 53.3 54.2 47.7 49 .2 47 .7

3 5 . 8 27.8 27.6 26.4 25.6 24.6 21.5 20 .4 19.0 1 6 . 8

9 . 3 2 0 . 5 10 .7 30.6 13.1 45 .6 9 . 4

35.2 38 .1

5 . 4

54 9, 51 , 61 7 43 0 61 3 29 8 69 1 44 1 42 9 77 8

56.4 42.9 50.7 3 7 . 0 68 .2 31 9 48 9 3 0 . 0 2 6 . 5 50.2

9 . 6 20 6 1 2 . 5 25 9

7 . 8 33 .3 1 4 . 8 30.7

11.8 3 3 . 1

34 0 36 5 3G 8 37 1 24 0 34 8 36 3 39 3 40 4 38 1

129.6 132.2 130 6 134.2 131.5 136.3 131.7 134.4 135.6 132.5

16 3 14 6 12 1 11 1 10 6 9 9 8 5 7 3 6 9 6 8

7 3 . 0 19.9 1 1 . 3 17 .8 24.8 63 .0 43.3 13.3 8 . 9 2 . 4

10 .7 6 5 , 5 76 .6 71, 1 63 .6 27.1 48 .2 79 4 84 2 90 8

22 6 29 9 32 8 25 5 21 5 13 5 14 8 21 5 25 1 40 0

58 .6 2 7 . 3 24 .9 30 .2 34 .4 48 7 42.2 3 3 . 8 28.9 1 1 . 5

18 8 42 8 32 3 41 3 44 1 37 8

44 , 46 0 48 5

43 .2

143,6 135.0 134 ,3 138.3 1 3 6 , l 143.2 141.3 136.7 136,6 136.4

6 4 90 9 2 7 9 0 82 4 8 G 150 9 31 5 62 2 13 1 40 9 46 0 6 3

4 4 84 3 11 3 5 9 70 6 23 6 139 4 146 6



TABLE XII. VAPOR COMPOSITION DATA FOR ACETONE-METHYL ETHYL KETONE-WATER

(At 250 pounds per square inch absolute) Liquid Vapor

Acetone, MEKa, Water, Acetone, MEKa, Water, mole % mole % mole % mole % mole % mole % Temp., O C.

78.2 71.3 67.4 62.0 61.5 61 .1 50.4 39.6 37.4 33 .8

32.0 26.9 25 .5 20 .7 20 .3 19 .0 17.9 17 .3 15 .3 14.1

10.5 21 .0 21.3 14 .1 31 .2 15.2 11 .9 25 .8 25.4

9 . 7

14 .7 10.9 46 .4 11 .5 35 .8 38.6 42 .7

3 .9 79.1 46 .3

11 .3 7 .7

11 .3 23.9

7 .3 23.7 37.7 34.6 37.2 56.5

53.3 62.2 28.1 67.8 43.9 42.4 39.4 78.8

5.6 39.6

78 .7 74 .3 69.4 65.2 67 .1 63.8 56.4 46.0 43.5 47.1

4 4 . 5 41.0 29.1 37.4 26.1 24.1 21 .1 42.0 19.2 43.2

6 .8 14 .3 14 .0 8.8

21.7 9 . 9 8 .5

18 .9 18.8 8 .9

13 .3 12 .2 34 .0 14 .9 29 .5 31.2 34 .2

7 .5 67.6 33.9

14 .5 11 .4 16.6 26.0 11.2 26.3 35.1 35.1 37.6 44.0

42.2 46.8 36.9 47.7 44 .4 44 .7 44 .7 50.5 13.2 22.9

171.2 175.7 175.3 171.4 178.7 171.7 171.9 175.0 174.9 172.8

173.9 174.0 177.6 175.1 176.9 177.6 178.0 174.5 193.4 180.6

5 9 93 3 0 8 7 3 87 8 4 9 201 7 3 3 21 5 75 1 f i ? 37 5 56 2 186.5 3 3 6 3 90 4 14 o 26 2 59 2 185 8


TABLE XIII. VAPOR COMPOSITION D.4TA FOR ACETONE-METHYL ETHYL KETONE-WATER

(At 500 pounds per square inch absolute) Liquid

Acetone, M E K ~ , WZ mole % mole % mole % __-

78 3 69 2 62 1 60 0 48 4 48 3 40 0 39 8 38 5 37 4 36 6 27 9 25 8 25 7 24 2 23 6 20 7 16 3 14 2 13 5

13 .8 24.6 17 .3 19 .5 27.8 10.8 27 .8

7 .1 51.0 27.3

18.4 9 .6

36.6 22.2 50.7 10.9 39.7

6.9 83.1 34.1

7 .9 6 . 2

20.6 20 .5 23.8 40.9 32 .2 53.1 10 .5 35 .3

46 .0 62.5 37 .6 52.1 25 .1 65.5 39.6 76.8 2 . 7

52 .4

12 .6 19.2 68.2 12.5 13.1 74 .4 10 .8 24.0 65.2 8.8 9 .3 81.9 5 . 3 18 .9 75.8 5 . 1 6 . 0 88.9 4.7 94.1 1 . 2 4 . 0 37.3 58 .7


Acetone, mole yo

78.7 72.6 62.2 60 .5 49.9 52.1 42 .6 47.7 40.5 39 .3

40.4 39.7 28.7 31 .3 26.6 34 .0 22.9 29.8 17 .0 16 .7

17 .5 22 .0 14 .9 18 .7 8 . 7

15 .8 6 . 9 5 .4

Vapor MEKa, mole yo

9 .9 18 .5 12 .8 14.4 20.3 8 . 7

20 .8 6.2

40.4 20.7 14 .7 9 . 8

28 .5 18 .3 42.1 11 .6 31 .5 10 .9 78.5 29.9

23.2 18.0 27.1 18.8 28.5 17.0 91.6 35.7

water , ‘ mole % Temp., C.

11 .4 213.6 8 , 9 218.5

25.0 212.3 25.1 212.8 29.8 215.6 39.2 209.2 36.6 214.1 46.1 209.6 19.1 225.4 40.0 214.1

44.9 211.4 50.5 211.2 42.8 215.9 50.4 214.0 31.3 219.4 54.4 212.8 45.6 216.4 59.3 214.4 4 . 5 241.7

53.4 216.4

59.3 215.6 60.0 216.5 5.8 . 0 216.0 62.5 216.1 37.2 221.1 67.2 221.0

1 . 5 247.3 58.9 225.7

TABLE XIV. VAPOR PRESSURES OF ACETONE AND METHYL ETHYL KETONE

Acetone Methyl Ethyl Ketone ______ Vapor pressure Vapor pressure.,

Temp., C. lb./sq. in. abs.’ Temp., C. Ib./sq. in. abs.

Griswold, J., and Dinwiddie, J. A., IND. ENG. CHEM., 34, 1188 (1942).

“International Critical Tables,” New York, McGraw-Hill Book Co., 1928.

Karr, A. E., Scheibel, E. G., Bowes, W. M., and Othmer, D. F., IND. ENQ. CHEM., 43, 961 (1951).

Keenan, J. H., and Keyes, F. G., “Thermody- namic Properties of Steam,” New York, John Wiley & Sons, 1936.

Lipkin, M. R., et al., IND. ENG. CHEM., ANAL. ED., 16, 55 (1944).

Marshall, A., J. Chem. Soc., 1906, 1350. Meissner, H. P., Chem. Eng. Progress, 45, 149

Othmer, D. F., IND. ENQ. CHEM., 32, 841

Othmer, D. F., IND. ENG. CHEM., ~ A L . ED.,

(1949).

(1940).

20. 763 (1948). (13) Othmer, D. F., ‘and Benenati, R. F., IND. ENG.

(14) Othmer, D. F., and Gilmont, R., Ibid., 36, 858

(15) Ibid., 40, 2118 (1948). (16) Othmer, D. F., and Morley, F. R., Ibid., 38,

751 (1946). (17) Othmer, D. F., Silvis, S. J., and Spiel, A,, Ibid.,

44, 1872 (1952). (18) Othmer, D. F., and Ten Eyck, E., Ibid., 41,2897

(1949). (19) Othmer, D. F., and Tobias, P., Ibid.. 34, 693

(1 942). (20) Perry, J., ed., “Chemical Engineers’ Hand-

book,” 3rd ed., New York, McGraw-Hill Book Co., 1950.

(21) Redlich, O., and Kister, A. T., IWD. ENG. CHEM., 40, 341 (1948).

(22) Ibid., p. 345. (23) Shell Chemical Corp., “Methyl Ethyl Ketone”

(24) Squibb, E. R., J . Am. Chem. Soc., 17, 189

(25) Stull, D. R., IND. ENG. CHEM., 39, 517 (1947). (26) Timmermans, J., and Martin, F., J . Chim.

phys., 25, 411 (1928). (27) Timmermans, J.. and Martin, F., PTOC. Roy.

Irish Acad., 13,333 (1912). (28) Treybal. R. E., Weber, L. D., and Daley, J.

F., IND. ENG. CHEM., 38, 817 (1946). (29) Watson, K. M., Zbid., 35, 398 (1943). (30) York, R., Jr., and Holmes, R. C., Ibid., 34, 345

CHEM., 37, 299 (1945).

(1944).

(1950).

(1895).

(1942).

RECEIVED for review April 21, 1951. ACCEPTED Fehruary 21, 1952.

Presented before the XII th International Congress of Pure and Applied Chemistry, September 1951, New York. Previous articles of this series have appeared in IND. ENO. CHEM,, 1928, 1943, 1944, 1945, 1946, 1947, 1948, 1949, and 1951: in IND. ENQ. Cnnnf., ANAL. ED., 1932. and in Anal. Chem. in 1948.

TABLE xv. VALUES OF THE CONSTANTS IN THE REDLICH AND KISTER CORRELATION FOR THE BINARIES AT VAR~OUS PRESSURES

Pressure, Lb /Sq In. Abs. a 0 0

-~ 14 7 50 100 250

SYSTEM: ACETONE-WATER B 0 715 0 680 0 640 0 681 0 490 C -0 084 -0 200 -0 190 -0 180 -0 220

SYSTEM: METHYL ETHYL KETONE-WATFR B 0.940 0.850 0.800 0.639 0.489 C -0,182 -0,240 -0.280 -0,280 -0,356 D 0.0924 0.0572 0.0408 0,0210 0.0047 E -0.129 -0.110 . . . . . . . . , , ..

Documents

Binary and Ternary Systems of Acetone, Methyl Ethyl Ketone, and Water